Manufacture of refractory metal borides



Patented May 18, 1954 UNITED STATES ATENT OFFICE MANUFACTURE OF REFRACTORY METAL BORIDES Hugh S. Cooper, Shaker Heights, Ohio, assignor to Walter M. Well, Cleveland, Ohio No Drawin Application June 21, 1950, I SerialNo. 169,530 H 20 Claims.

prepared in anything approaching a pure form.

This is probably duein part to the unavailability of sufficiently pure elemental boron for use as a starting material and in part to the numerous technical problems involved in producing borides by the known methods.

The borides of calcium, carbon, and chromium have been made by reduction'of borates or boron oxide with carbonsilicon, or aluminum, either in anarc furnace or by thermic means. When these borides are prepared by such procedures,

however, the product always contains appreciable impurities, and little is known about-thetrue properties of these compounds. r

In my copendingapplications Serial No. 120,414, now Patent No. 2,572,248, for Methods of Making Boron and Serial No. 120,415, now

abandoned, for Production of Boron, both filed October 8, 1949,'and Serial No. 169,529 filed June 21,- 1950, now Patent No. 2,572,249, for Production of Elemental Boron, I have-disclosed commercial methods of making elemental boron "from about 96% to better than 99 purity. With the availability of elemental boron-of such purity, the possibilitiesfor numerous uses therefor have been opened up. Among the possibilities which I have investigated is the production of refractory metal borides, and particularly the borides of titanium, zirconium, thorium, columbium, and tantalum, in a commercially useful, 'finely= powdered form. The present invention relates specifically to the production of such refractory metal borides using elemental boron as one of the starting materials. I r

Tantalum and columbium, for example, in elemental form, are obtainable only as coarse, granular powders and, if. converted directly into borides by reaction withboron at elevated temperatures, would yield compounds equally coarse and extremely difiicult to reduce to a fine powder "without serious contamination during the grind- "lng operation. Zirconium-and titanium, on the 2 other hand, are too active chemically to be used in the elemental state.v Because of their extreme activity, both of these metals, whenin granular or finely divided form, are required to be shipped in a water-wet condition. It is impractical, there fore, to use any of these metals intheirelemental forms as starting materials in the production of their borides. Also, because of the stability of their oxides, reaction of the oxides with boron is virtually impossible,

I have found that the borides of titanium, zirconium, thorium, columbium, and tantalum, however, may be formed by starting with the hydrides of these refractory metals, which are air stable and are obtainable commercially in a finely divided form. The vhydrides of titanium, zirconium, thorium, columbium, and tantalum are readily produced by. reduction of their oxides with cal-- cium hydride. vThe resulting hydrides of these refractory metals begin to break down and evolve hydrogen at temperatures aboveaboutGOOfCn and at about 1400 C., very little, if any, hydrogen is retained thereby. During this break down, the

free metal is liberated in nascent form.

According to the present invention, the hydride of any of these refractory metals mentioned, in a finely divided form preferablysmaller than 300 mesh, is first thoroughly mixed in about stoichiometric proportions with powderedboron of similar fineness, and the mixture is pressed into small briquettes. While thesijze of the briquettesis not critical, I prefer that they be about 1%, inches, in .their largest linear dimension and Weigh about 50 grams when using the small equipment hereinafterdescribed. r r v A suitable furnace chamber is heated to atomperature of about 1000 to about O C. and

scavenged with hydrogengastoremove an oxygen and provide a hydrogen atmosphere therein.

The previously. prepared briquettes arefthen dropped into the furnace in relatively smallduam titles, which may vary accordingto the volume of the furnace chamber and the particular metal hydridefeinployed. The hydride quickly decomposes at the high furnace temperature, and} the metal of the hydride combines directly and'exothermically with the boron to produce the corresponding metalboride. h

In the case of titanium hydride, the decomposition of the hydride and reaction with the boron is very violent and highly exothermic, and it is for this reason that only small amounts of the hydride are introduced at a time into a previously heated furnaca r'ather than putting the it up to the reaction temperature. When using zirconium hydride, the reaction is somewhat less violent and less exothermic, though still enough to render the portionwise addition of the briquettes highly desirable to avoid blowing the charge out of the furnace. The other refractory metals of present interest, namely, thorium, columbium, and tantalum, appear to be quite comparable with zirconium in the violence of their reactivity with boron and may be charged into the furnace in similar quantities. The larger the furnace chamber, of course, the larger is the amount of charge that can safely be introduced at one time.

After each addition of a portion of the total furnace charge, the reaction is allowed to subside before the next addition is made. Since the reaction is exothermic in all cases, the furnace temperature will generally rise sharply during the process and may reach a point several hundred degrees above the prevailing temperature at the time of the first addition of charge material. When charging of the briquettes into the furnace has been completed, the temperature of the furnace is preferably maintained at about 1500 to 160% C. for a soaking period of about one to two hours to insure completion of the reaction. The application of heat is then terminated to permit the mass to cool to room temperature in the furnace chamber, the hydrogen atmosphere preferably being maintained during most of the required cooling time.

Upon removal from the furnace, the reaction mass is in the form of gray, crystalline, fairly coherent agglomerates which may be pulverized and sifted for size grading to put the product in suitable form for use. Because of their extreme hardness, these refractory metal borides give promise of great utility for most of the present uses of the various, hard, metal carbides. They should be highly useful in finely divided form as optical polishing materials, as abrasives in compacted and sintered form, with or without binding or cementing agents, and as materials of construction by powder metallurgical methods in the production of wear resistant dies, tools, and machine parts of various kinds.

For a better understanding of the invention, reference may be made to the following illustrative examples of the preparation of refractory metal borides. In each of these examples the apparatus consisted of an electrical resistance furnace in the form of a vertically disposed Alundum tube wrapped with a molybdenum resistance wire, the whole being encased in a heat insulating outer shell enclosing the sides and bottom of the Alundum tube. The open top of the Alundum tube was adapted to receive a cylindrical crucible for holding the reaction materials, and an Alundum crucible having inside dimensions of about 1%, inches in diameter and 6 inches in height was employed in Examples 1 and 2. Hydrogen gas was introduced into the furnace through its base in a constant stream. A flreclay cover having an exhaust tube therein was placed over the top of the furnace and hydrogen gas issuing from the exhaust tube was burned as a continuous flame. Additions of charge material to the crucible were made by sliding the cover partially to one side, dropping in the charge material, and sliding the cover back in place. The hydrogen escaping around the side of the cover during this operation ignited from the exhaust tube flame and burned freely thus indicating an adequate supply of hydrogen in the furnace.

Example 1 250 grams of titanium hydride powder (analyzing 99% pure) and 58 grams of elemental boron powder (analyzing about 96% pure) were thoroughly mixed together in a small ball mill. The powders were about the same in particle size, both being less than 325 mesh. Slightly more than the stoichiometric amount of boron was used to allow for assumed minor inaccuracies in the analysis of the boron and any slight loss of elemental boron that may have been due to oxidation. The intimately mixed powders from the ball mill were pressed into briquettes in the form of discs about 1% inches in diameter and about inch thick and weighing about 50 grams. The furnace was brought up to a temperature in the range of l250 to 1350 0., and the entire quantity of the previously prepared briquettes was added portionwise, about 50 grams at a time at 15 minute intervals, each briquette being broken in half just before dropping it into the crucible. These intervals were sufficient for the almost explosive reaction to subside after each addition. By the time all of the material had been added, the temperature had risen to about 1700 C., and was held at about 1600 C. for another two hours to insure completion of the reaction. Because of the highly exothermic nature of the reaction, it was obvious that it must have gone substantially to completion.

Because of the extreme properties of the titanium boride produced as described, many of its properties are most difiicult to measure. It is extremely resistant to the common single acids, though it can be dissolved with a mixture of nitric acid and hydrofluoric acid. Its hardness is above 9 on the Mohs scale, being, roughly comparable in hardness to tungsten carbide. Its melting point is above 3000 C., compared to a melting point of about 3000 C. for zirconium boride, one of the highest melting metal compositions tested heretofore for use in making certain parts in jet propulsion and rocket propulsion power plants.

Based on the use of 1 mol of titanium and 1 mol of boron in making this material, and upon the exothermic reaction that obviously went to completion, the product may be represented by the formula TiB, as noted above, though it may be questionable whether the product is accurately represented by this formula. That a true chemical combination of titanium and boron occurred is certain. However, the literature on metal borides is so meager and so indefinite, and the analysis problem is so difficult that positive identification of the formula for the product is not possible at this time. For instance, the product could be a solution of TiBz in titanium. In view of this uncertainty, I prefer to define the product, which I believe to be novel, as a homogeneous, substantially pure, combination of titanium and boron, though, for simplicity, the product is also referred to herein as titanium boride or a boride of titanium.

Example 2 ZrHz+2B+ZrBz+H2 (probable) 400 grams of zirconium hydride powder (analyzing 99% pure) and 100 grams of boron (analyzing about 98% pure) were thoroughly mixed in a ball mill and briquetted in the same manner perature rise during'the reaction was substantiallyless than in Example 1, reaching only about The zirconium boride product was similar in appearance to thetitanium boride; product in Example 1; and was pulverized and sifted, yield- 99% of'material finer than '200-mesh, the

remainderbeing retained on a 100 mesh screen.

Examplev 3 '-TaH+2B TaBz+H (probable) 24Lgrams oftantalum hydride powderlanalyzing 99% pure) and 32 grams of boron (analyzing about 96% pure) were thoroughly mixed and briquetted as .in the preceding .examples, and the briquettes were addedto a similar, but smaller, furnace in the same manner as before while'employing the same starting temperature .in. the furnace. In this example the Alundum crucible was 1 inch in inside diameter and 3 inches deep. The heat of the reaction raised the furnace temperature to about 1600 C. -The product was similar in appearance to the products of Examples 1 and 2-and was readily reduced to a powder. passing through a 200 mesh screen.

Examplcal ThH+2B ThBz+I-I (probable) 23.3 gramsof thorium hydride powder (analyzing better"than99% pure) and 2 grams of boron (analyzing about 99.5% pure) were thoroughly mixed and pressed into a single small briquette which was added in one piece the same soaking time and temperature were employed as before. The thorium. boride, productwassimilar in appearance tothe products of 'the preceding examples and wasreadily reduced to apowder passing through a. 200.. mesh screen.

Example 5 18.8 grams of columbium hydride powderianalyzing 99% pure) and 4.4 grams of boron (analyzing about 99.3% pure) were thoroughly mixed, briquetted, and added to the small furnace in the same manner as in Example 4, while employing the same procedure and furnace temperatures. As in the previous examples, the reaction demonstrated itself to be exothermic, the heat of the reaction causing a substantial rise in the furnace temperature. The columbium boride product was similar in appearance to the products of the preceding examples and was readily reduced to a powder passing through a 200 mesh screen.

In Examples 2 to 5, as in Example 1, the products were very hard, high melting, and highly inert. The same problems exist in positively identifying the product formulae, though there is somewhat more evidence in the literature that the probable product formula given in each of the last four examples is the correct one. It

6 should be understood that, throughout-thislapplication, the term boride is necessarily used somewhat loosely in view of the uncertainties as to the exact composition of the products made. From the foregoing description of the invention, -it-will be apparentthat I have. discovered a simple-and effective procedure for;producing substantially pure homogeneous, chemicalcom- --binations of boron with a number of refractory 10" The character of the reaction and the reactants employedaresuch that there is very littleoppormetals'that are capable of forming hydrides.

tunity for contaminationof the -product,.andthe purity ofthe products is substantially the same as the purity of the ingredients employed. The

fineness of the particle size of theproducts renders them highly suitable for most of the in- ''dustrialuses for extremely hard and inert compounds of this general character.

' While I have referred specifically to producing chemical combinations of boron with titanium, zirconium, thorium columbium, and

tantalum, it will be noted that these last-five metals all fall in either group IVaor. Va of the --periodic-table. For purposes of definition of the invention, therefore, the methods disclosed may be said to be suitable for reacting boron with those-metals which are capable of forming hydrides andwhich fall in groups IVw-and Va of the periodic table.

While the invention has been illustrated by reference to certain specific examples, it-will be --understood that the details of theprocedures described may be varied-without departing from thetrue spirit andscope of the invention as defined in the appended claims.

I claim:

- 1. The method of making metal borides which comprises introducing an intimate mixture of elemental boron and the hydride ofa metal selected from the class consisting of titanium, zirconium,-thorium, columbium, and tantalum into-an atmosphere consisting substantially en- --tirely-of hydrogen'in a furnace chamber preheated to a temperature, in the range from about 1000" to about 2000 (3., sufficient to decompose "the hydride and effect combination of the boron elemental boron and and said selected metal.

2. Themethod of making metal borides which comprises introducing an intimate mixture of the hydride of a metal selected from the class consisting of titanium,

- zirconium, thorium,

columbium, and tantalum Q into an atmosphere consistingsubstantially en- 1000", to about 2000 -tirely-of hydrogen in a furnace chamber preheated to a temperature, in the range fromfabout (3., suificient to decompose the hydride and effect combination of theboron and said selected metal, and maintaining the temperature in said range until reaction between the two metals has subsided.

3. The process of claim 2 in which said intimate mixture is in the form of briquetted powders of the component materials.

4. The process of claim 2 in which said intimate mixture is in the form of briquetted powders of the component materials present in substantially stoichiometric proportions.

5. The process of claim 2 in which said intimate mixture is in the form of briquetted powders of the component materials present in substantially stoichiometric proportions, the briquetted mixture being introduced portionwise at intervals into said hydrogen atmosphere to mini- --'miz =the explosive" violence of the resulting re- 1 action.

6. 'The-=method-of-- making, borides= of metals from groups IVaand-Va of the periodic'table which are capable of' forming hydrides, said method comprising providing an atmosphere "consisting substantially entirely of hydrogen in an--enclosed furnace'chamberpre heated to a *"temperature -in-therange from about l0 0( )'C. to about 2000-C., and introducing into saidhy- -drogenatmosphereat' intervals a br-iquetted intimate mixture of; powders of elemental boron -and-one of said hydrides.

7. The-methodofclaim 6 in istitanium hydride.

*8. Themethod of claim 6 in which the hydride is zirconium'hydride.

'9. Themethod of claim 6- in is thorium hydride.

-'-l0."The method of claim 6- in which the hydride-is columbium -hydride.

-11: The-method of claim din which "the hydride is tantalum hydride.

' 12. The method of making borides ofmetals from groups IVa andVa of theperiodic table which are capable of forming hydrides, said methodcomprising providing an atmosphere consisting substantially entirely of hydrogen in an enclosed furnace chamber pre-heated toatemperature in the range from-about 1 000 C. to about 2000 C.,- and introducinginto said hydroi: gen-atmosphere-at intervals a briquetted inti- --mate mixture of powders of elemental boron and ons of 'saidhydrides; permitting the temperature 'within'said-chamber to rise from-the resulting exothermic reaction andmaintaining the temperature of said furnace chamber above the -'minimum of said range until said reaction has subsided while also maintaining the hydrogen atmosphere therein.

' 1-3.- A method for making borides of titanium,

- zirconium, thorium, columbium, and tantalum which comprises introducing an intimate mixture of a hydride of one of saidmetals with elemental boron into an atmosphere consisting'substantially entirely of hydrogen in afurnace chamber pre heated toa temperature in the range-of about 1G00 to about 2D0O C.

14. A method for making borides of titanium, Zirconium, thorium, columbium and tantalum whiizhcbmpfises introducing an intimate mixture 4 of-a hydride of one of said metals witheleme ntal which the hydride whichthe hydride or'on "into an atmosphere consisting substantiaily entirely of hydrogen ina furnace chamber pre heated to a temperature in the range of about 1000 to about 2000 C., said mixture being in the form of finely divided powders of the components thereof pressed into briquettes.

' said" mixture being 'in the -15. A method suitable for making borides of titaniumf Z ircon i umQ thorium," dommbiu 'i and ia aiu w i i si i i s fi di i g n i imate mixture of a hydride of'oneof saidmetals with elemental boron into an atmospherecom sisting substantially entirely" of hydrogen 'in'a atmoisphere incr'ementally at'int'ervals to"r ni'nimize the explosive violence ofthe resulting exothermic boride' forming reaction, and maintaining the temperatureoi said furnace chamber above about 1400" C. until said reaction has 'f'r'eached substantial completion followingthe "last addition of reactants.

1s. The method" of claim is'in-whicn-"th hydride is titanium hydride. V I

, 17. The method of 'clairn 15 in whichthe hydr'ide is zirconium hydride.

l8.'The method of claim dride' is thorium hydride. I

f" lQFEhe'me'thOd'of claim 15 in which the hy- 15 in which the 'hydridelj is" columbium hydride.

, '20.'"'rhe iriethodof claim '15'in which the hydri'de is tantalum hydride.

*aererm es Cited in-"tl ie-file of'this patent UNITEDsTATEs'PA'rENTs Number Name Date 1,129,507 Peacock ..'Fb. 23, 1915 1,835,024 Driggs ,Dec. 8, 1931 2,534,676 Newton 'et al. Dec. 19,1950

OTHER REFERENCES Nossan, Comptes Rendus,"yolumei i20, pages 401290-296 at 293, (1895) (Copy inscienufic Library) v. Tucker, et al., Journal of the Chemical Sofci ejtyjjvoluirie;81, pages 14-17, (1902) (Copy in Scientific Library.)

Zalkin et a1.,1The C1jys'tal Structure "of g m,

rem n ong atqmic energ Commission Des'sion, Technical "Information 

1. THE METHOD OF MAKING METAL BORIDES WHICH COMPRISES INTRODUCING AN INTIMATE MIXTURE OF ELEMENTAL BORON AND THE HYDRIDES OF A METAL SELECTED FROM THE CLASS CONSISTING OF TITANIUM, ZIRCONIUM, THORIUM, COLUMBIUM, AND TANTALUM INTO AN ATMOSPHERE CONSISTING SUNSTANTIALLY ENTIRELY OF HYDROGEN IN A FURNACE CHAMBER PREHEATED TO A TEMPERATURE, IN THE RANGE FROM ABOUT 1000* TO ABOUT 2000* C.,SUFFICIENT TO DECOMPOSE THE HYDRIDE AND EFFECT COMBINATION OF THE BORON AND SAID SELECTED METAL. 